N-(2-chloro-phenyl)-N'-phenyl-formamidine | 101649-75-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: N-(2-chloro-phenyl)-N'-phenyl-formamidine
• 英文别名: N-(2-Chlor-phenyl)-N'-phenyl-formamidin；N'-(2-chlorophenyl)-N-phenylmethanimidamide
• CAS: 101649-75-6
• 化学式: C₁₃H₁₁ClN₂
• 分子量: 230.697
• InChiKey: ZDGJUOZXJOBYPC-UHFFFAOYSA-N

物化性质

• 熔点：
  113 °C(Solv: methanol (67-56-1))
• 沸点：
  362.5±44.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  24.4
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  邻氯苯胺 生成 N-(2-chloro-phenyl)-N'-phenyl-formamidine
  参考文献：
  名称：

  THE STRUCTURE OF THE SOLID REACTION PRODUCT OF ANILINES AND ETHYL ORTHOFORMATE^1,2

  摘要：

  DOI：

  10.1021/jo01157a023

文献信息

• N,N'-diphenyl-N-(N"-alkylcarbamoyl)formamidines
  申请人：Sandoz Ltd.

  公开号：US03966805A1

  公开（公告）日：1976-06-29

  The present invention concerns novel N,N'-diphenyl-N-(N"-alkylcarbamoyl)formamidine derivatives of the formula: ##EQU1## wherein R.sub.1 is hydrogen or alkyl, R.sub.2 is alkyl and Ar.sub.1 and Ar.sub.2 are each phenyl or a substituted phenyl, which compounds are useful as herbicides. The present invention relates to N,N'-diphenyl-N-(N"-alkylcarbamoyl)formamidine derivatives. The present invention provides compounds of formula I, ##EQU2## wherein R.sub.1 is hydrogen or alkyl of 1 to 4 carbon atoms, R.sub.2 is alkyl of 1 to 4 carbon atoms, and either Ar.sub.1 and Ar.sub.2 are the same, and are each phenyl or a substituted phenyl group selected from ##SPC1## Wherein R.sub.3 is chlorine, bromine, methyl, methoxy, or dimethyl or diethylsulphonamide and R.sub.4 is chlorine, bromine, methyl, methoxy or trifluoromethyl, or Ar.sub.2 is phenyl and Ar.sub.1 is a substituted phenyl group selected from ##SPC2## Wherein R.sub.3 ' is chlorine or methyl and R.sub.4 ' is chlorine, methyl or trifluoromethyl, With the proviso that Ar.sub.1 and Ar.sub.2 are other than ##SPC3## When R.sub.1 or R.sub.2 is alkyl, this is preferably of 1 to 3 carbon atoms, e.g. methyl, ethyl, n-propyl or i-propyl, and more preferably is methyl. The present invention also provides a process for the production of a compound of formula I which comprises A. REACTING A COMPOUND OF FORMULA IIa ##EQU3## wherein Ar.sub.1 and Ar.sub.2 are as defined above and M is a salt forming atom or group, preferably an alkali metal, especially sodium, With a compound of formula III, ##EQU4## wherein R.sub.1 and R.sub.2 are as defined above, or B. REACTING A COMPOUND OF FORMULA IIb, Ar.sub.1 --N=CH--NH--Ar.sub.2 IIb wherein Ar.sub.1 and Ar.sub.2 are as defined above, with a compound of formula IV, r.sub.2 --n=c=o iv wherein R.sub.2 is as defined above, to product a compound of formula Ia, ##EQU5## wherein Ar.sub.1, Ar.sub.2 and R.sub.2 are as defined above. The process of the invention, in accordance with variant (a) above, may be effected as follows: A compound of formula IIa may be dissolved or suspended in an inert solvent or suspension medium and a compound of formula III, which may also be dissolved or suspended in an inert solvent or suspension medium, added thereto. Examples of suitable solvents or suspension media are hexamethyl phosphoric triamide or benzene. The reaction may conveniently be effected at room temperature, preferably over a prolonged period e.g. 12 hours, and conveniently with stirring. Working up may be effected in conventional manner. In a preferred modification of the process variant described above, the compound of formula IIa is produced in situ and without isolation, from a compound of formula IIb, by reaction with a strong base, e.g. sodium hydride. The process may be effected by adding a compound of formula III, which may be dissolved or suspended in a suitable solvent or suspension medium to a mixture of a compound of formula IIb and a strong base, in an inert solvent or suspension medium. Examples of suitable solvents or suspension media are hexamethyl phosphoric triamide or benzene. The reaction may then be effected as described above. With respect to the working up of the reaction mixture, excess of the strong base, e.g. sodium hydride, is carefully decomposed, for example, by the addition of water while cooling with ice. In the case where a water immiscible solvent or suspension medium is employed, addition of water may be continued until well separated phases have been obtained. Further working up may be effected in conventional manner. The process of the invention in accordance with variant (b) above, may be effected as follows: A compound of formula IV is added to a compound of formula IIb in an inert solvent, such as absolute toluene, and the mixture is reacted at an elevated temperature, e.g. 80.degree.C, and at an elevated pressure. The mixture may be allowed to react over a prolonged period, e.g. 60 hours. The reaction is preferably effected in an autoclave. Working up is effected in conventional manner. The compounds of formula I are, in general, colourless crystalline substances. Purification may be effected by recrystallisation from suitable solvents, e.g. ethyl acetate or an ethyl acetate/hexane mixture. The compounds of formula IIa, employed as starting material in process variant (a), may be obtained as described above, from a compound of formula IIb, by reaction with a strong base, e.g. sodium hydride. The compounds of formula IIb, employed as starting material in process variant (b), and also in the production of a compound of formula IIa, may be obtained in manner known per se, a' by reacting a compound of formula V ar.sub.1 --N=CH--O--R.sub.5 V wherein Ar.sub.1 is as defined above and R.sub.5 is alkyl of 1 to 4 carbon atoms, preferably ethyl, with a compound of formula VI, h.sub.2 n--ar.sub.2 VI wherein Ar.sub.2 is as defined above, or b' by reacting two equivalents of a compound of formula VI with one equivalent of a compound of formula VII, ch(or.sub.6).sub.3 vii wherein R.sub.6 is alkyl is 1 to 3 carbon atoms, preferably ethyl, to produce a compound of formula IIb' Ar.sub.1 '--N=CH--NH--Ar.sub.2 ' IIb' wherein Ar.sub.1 ' and Ar.sub.2 ' have the same significances as Ar.sub.1 and Ar.sub.2 respectively, defined above, with the proviso that Ar.sub.1 ' is the same as Ar.sub.2 '. The compounds of formulae III, IV, V, VI and VIII are either known or, insofar as they are not known, they may be produced in analogous manner to the processes for the production of the known compounds. The compounds of formula I are useful because they possess biological activity in plants. In particular the compounds of formula I are useful as herbicidal agents, as indicated in the following test viz: Test 1 The compounds were applied to cultures of the weed species Amaranthus retroflexus, Capsella bursa pastoris, Chenopodium album, Galium aparine, Stellaria media, Senecio vulgaris, Echinochloa crus-galli, Alopecurus myosuroides and Agrostis alba post emergence, at concentrations of 21/2 and 3 kg/hectare. The cultures were examined 14 days after application. A significant herbicidal effect was observed against each of the weeds at the concentrations tested. In addition, the compounds of formula Ib, ##EQU6## wherein Ar.sub.1 " and Ar.sub.2 " are the same and are each a substituted phenyl group selected from ##SPC4## wherein R.sub.3 " and R.sub.4 " are each chlorine, bromine or methyl, and the compounds of formula Ic, ##EQU7## wherein Ar.sub.1 '" and Ar.sub.2 '" are the same and are each a substituted phenyl group selected from ##SPC5## are further useful as selective herbicidal agents in combating weeds in cotton and potato cultures respectively, as indicated by the following tests: Test 2 In the case of the compounds N,N'-di-(4-chlorophenyl)-N-(N"-methylcarbamoyl)-formamidine and N,N'-di-(3,4-dichlorophenyl)-N-(N"-methylcarbamoyl)-formamidine, Test 1 was conducted in a potato culture containing the abovementioned weeds, post emergence, at a concentration of 3 kg/hectare of the compounds. No significant effect on the potatoes was observed at the concentration tested whereas a significant effect was observed against the weeds. Test 3 Compounds of formula Ib, were tested in cotton cultures (Gossypium hirsutum) containing the following weeds species Sida spinosa, Echinochloa crus galli, Amaranthus retroflexus, Ipomoea rubra, Digitaria sanguinalis, Chenopodium album, Sisymbrium irio and Postulaca oleracea. The compounds were applied at a concentration of 3 kg/hectare pre-emergence and 21/2 kg/hectare post emergence. In both cases, a significant herbicidal effect against the weed species was observed with no significant effect on the cotton crop. The preferred compounds of formula I are the compounds of formulae Ib and Ic. Particularly interesting compounds of formula Ib are the compounds N-n'-di-(3-chlorophenyl)-N-(N"-dimethylcarbamoyl)-formamidine, N,n'-di-(4-chlorophenyl)-N-(N"-dimethylcarbamoyl)-formamidine, N,n'-di-(4-bromophenyl)-N-(N"-dimethylcarbamoyl)-formamidine, N,n'-di-(3-methylphenyl)-N-(N"-dimethylcarbamoyl)-formamidine and N,n'-di-(4-methylphenyl)-N-(N"-dimethylcarbamoyl)-formamidine. However, other groups of compounds falling within the scope of formula I may also be mentioned as having interesting properties, e.g. the compounds of formula Id, ##EQU8## wherein R.sub.1.sup.IV is alkyl of 1 to 4 carbon atoms, R.sub.2.sup.iv is alkyl of 1 to 4 carbon atoms and Ar.sub.1.sup.IV and Ar.sub.2.sup.IV are the same and are each phenyl or a substituted phenyl group selected from ##SPC6## wherein R.sub.3.sup.iv is chlorine, methoxy or diethylsulphonamide and R.sub.4.sup.iv is chlorine, methoxy or trifluoromethyl with the proviso that Ar.sub.1.sup.IV and Ar.sub.2.sup.IV are other than ##SPC7## and the compounds of formula Ie, ##EQU9## wherein R.sub.1.sup.V is alkyl of 1 to 4 carbon atoms, R.sub.2.sup.v is alkyl of 1 to 4 carbon atoms, Ar.sub.2.sup.V is phenyl and Ar.sub.1.sup.V is a substituted phenyl group selected from ##SPC8## wherein R.sub.3.sup.v is chlorine or methyl and R.sub.4.sup.v is chlorine or methyl. For the abovementioned uses, the amount of compound to be applied to a weed infested locus will vary depending on the particular compound employed, mode of application, ambient conditions, the weeds species to be combated and the cultivated crop, if any, involved. However, in general, a suitable amount to be applied to a locus is between 1 and 10 kg/hectare of the compound, the application to be repeated as required. The compounds may be employed as herbicidal compositions in association with herbicide carriers or diluents. Such compositions also form part of the present invention. Herbicidal compositions may be employed in either solid or liquid application forms. Solid forms, e.g. dusting forms and granulates, may be produced by mixing or impregnating solid herbicide carriers such as diatomaceous earth, kaolin, talc, chalk, limestone and cellulose powder, with the compounds. Additives may be employed in the herbicidal composition. Typical of such additives are wetting and dispersing agents, e.g. the condensation product of formaldehyde with naphthalene sulphonate, and alkyl benzene sulphonates, adhesion imparting agents, e.g. dextrin, and emulsion stabilizers, e.g. ammonium caseinate. Such additives are suitable for incorporation into, e.g. a wettable powder form of composition. the herbicidal compositions may contain, aside from a compound of formula I as active agent, other active agents, such as herbicides, e.g. of the urea class, halogen benzonitriles, carbamates and triazines. Concentrate forms of composition generally contain between 2 and 80%, preferably between 2 and 50%, by weight of a compound of formula I as active agent. Application forms of composition generally contain between 0.01 and 10%, by weight of a compound of formula I as active agent.

  本发明涉及新颖的N,N'-二苯基-N-(N"-烷基氨甲酰)甲酰胺衍生物，化学式如下：##EQU1## 其中R.sub.1为氢或烷基，R.sub.2为烷基，Ar.sub.1和Ar.sub.2分别为苯基或取代苯基，这些化合物可用作除草剂。本发明涉及N,N'-二苯基-N-(N"-烷基氨甲酰)甲酰胺衍生物。本发明提供化合物的化学式I，##EQU2## 其中R.sub.1为1至4个碳原子的氢或烷基，R.sub.2为1至4个碳原子的烷基，Ar.sub.1和Ar.sub.2要么相同，分别为苯基或从中选择取代苯基，其中R.sub.3为氯、溴、甲基、甲氧基、二甲基或二乙基磺酰胺，R.sub.4为氯、溴、甲基、甲氧基或三氟甲基，或Ar.sub.2为苯基且Ar.sub.1为从中选择的取代苯基，其中R.sub.3'为氯或甲基，R.sub.4'为氯、甲基或三氟甲基，但Ar.sub.1和Ar.sub.2不能为##SPC3## 当R.sub.1或R.sub.2为烷基时，最好为1至3个碳原子，例如甲基、乙基、正丙基或异丙基，更好地是甲基。本发明还提供一种制备化合物I的方法，包括A.将化合物IIa的反应，其中Ar.sub.1和Ar.sub.2如上定义，M为形成盐的原子或基团，最好为碱金属，特别是钠，与化合物III的反应，其中R.sub.1和R.sub.2如上定义，或B.将化合物IIb的反应，Ar.sub.1 --N=CH--NH--Ar.sub.2 IIb其中Ar.sub.1和Ar.sub.2如上定义，与化合物IV的反应，r.sub.2 --n=c=o iv其中R.sub.2如上定义，产生化合物Ia的方法，##EQU5## 其中Ar.sub.1、Ar.sub.2和R.sub.2如上定义。根据上述变体(a)的本发明方法可如下进行：将化合物IIa溶解或悬浮在惰性溶剂或悬浮介质中，并加入化合物III，后者也可溶解或悬浮在惰性溶剂或悬浮介质中。适合的溶剂或悬浮介质的例子是六甲基膦酸三胺或苯。反应可以在室温下方便地进行，最好在较长时间内进行，例如12小时，并方便地搅拌。工作可能以常规方式进行。在上述过程变体的首选修改中，化合物IIa可以在原位且不经分离地由化合物IIb与强碱（例如氢化钠）反应而生成。该过程可通过将化合物III（可以溶解或悬浮在适当的溶剂或悬浮介质中）加入到化合物IIb和强碱的混合物中，在惰性溶剂或悬浮介质中进行。适合的溶剂或悬浮介质的例子是六甲基膦酸三胺或苯。然后，反应可以如上所述进行。关于反应混合物的处理，过量的强碱（例如氢化钠）应小心分解，例如通过在冰上冷却的同时加入水。如果使用不与水相混的溶剂或悬浮介质，则可以继续添加水直到获得明显分离的相。进一步的工作可能以常规方式进行。根据上述变体（b）的本发明方法可如下进行：将化合物IV加入到化合物IIb中，在惰性溶剂中，例如绝对甲苯，并在较高温度下（例如80度C）和较高压下反应。混合物可以在较长时间内（例如60小时）反应。最好在高压釜中进行反应。工作可能以常规方式进行。化学式I的化合物通常为无色结晶物质。纯化可以通过从适当的溶剂中（例如乙酸乙酯或乙酸乙酯/己烷混合物）结晶得到。作为过程变体（a）中的起始物质的化合物IIa可如上述方法获得，从化合物IIb通过与强碱（例如氢化钠）反应。作为过程变体（b）中的起始物质的化合物IIb，以及在化合物IIa的生产中，可以按照已知的方法获得，通过a'通过将化合物V ar.sub.1 --N=CH--O--R.sub.5 V其中Ar.sub.1如上定义，R.sub.5为1至4个碳原子的烷基，最好为乙基，与化合物VI，h.sub.2 n--ar.sub.2 VI其中Ar.sub.2如上定义，或b'通过将两当量的化合物VI与一个化合物VII，ch(or.sub.6).sub.3 vii其中R.sub.6为1至3个碳原子的烷基，最好为乙基，反应，以产生化合物IIb' Ar.sub.1 '--N=CH--NH--Ar.sub.2 ' IIb'其中Ar.sub.1 '和Ar.sub.2 '的含义与上述定义的Ar.sub.1和Ar.sub.2相同，但Ar.sub.1 '与Ar.sub.2 '相同。化合物III、IV、V、VI和VIII的化合物或已知，或者在不知道的情况下，可以类似于已知化合物的生产过程而制备。化合物I之所以有用，是因为它们在植物中具有生物活性。特别是化合物I作为除草剂是有用的，如下所示：测试1将化合物应用于后发生的杂草物种Amaranthus retroflexus、Capsella bursa pastoris、Chenopodium album、Galium aparine、Stellaria media、Senecio vulgaris、Echinochloa crus-galli、Alopecurus myosuroides和Agrostis alba的培养物中，浓度为每公顷21/2和3公斤。在施用后14天检查培养物。在测试的浓度下，对每种杂草都观察到显著的除草效果。此外，化合物Ib的化合物，##EQU6## 其中Ar.sub.1"和Ar.sub.2"相同，分别为从中选择的取代苯基，##SPC4## 其中R.sub.3"和R.sub.4"分别为氯、溴或甲基，以及化合物Ic，##EQU7## 其中Ar.sub.1'"和Ar.sub.2'"相同，分别为从中选择的取代苯基，##SPC5## 进一步作为选择性除草剂，在棉花和马铃薯培养中对抗杂草是有用的，如以下测试所示：测试2将N,N'-二-(4-氯苯基)-N-(N"-甲基氨甲酰)甲酰胺和N,N'-二-(3,4-二氯苯基)-N-(N"-甲基氨甲酰)甲酰胺的化合物应用于含有上述杂草的马铃薯培养中，后发生，化合物的浓度为每公顷3公斤。在测试的浓度下，未观察到对马铃薯的显著影响，而对杂草观察到了显著效果。测试3将化合物Ib的化合物应用于（Gossypium hirsutum）棉花培养中，含有以下杂草物种Sida spinosa、Echinochloa crus galli、Amaranthus retroflexus、Ipomoea rubra、Digitaria sanguinalis、Chenopodium album、Sisymbrium irio和Postulaca oleracea。化合物在前发生时浓度为每公顷3公斤，在后发生时浓度为每公顷21/2公斤。在两种情况下，对杂草物种观察到显著的除草效果，对棉花作物没有显著影响。化学式I的首选化合物是化学式Ib和Ic的化合物。化学式Ib的特别有趣的化合物是N-二-(3-氯苯基)-N-(N"-二甲基氨甲酰)甲酰胺、N,n'-二-(4-氯苯基)-N-(N"-二甲基氨甲酰)甲酰胺、N,n'-二-(4-溴苯基)-N-(N"-二甲基氨甲酰)甲酰胺、N,n'-二-(3-甲基苯基)-N-(N"-二甲基氨甲酰)甲酰胺和N,n'-二-(4-甲基苯基)-N-(N"-二甲基氨甲酰)甲酰胺。然而，化学式I范围内的其他化合物类别也可以被提及为具有有趣的性质，例如化学式Id的化合物，##EQU8## 其中R.sub.1.sup.IV为1至4个碳原子的烷基，R.sub.2.sup.IV为1至4个碳原子的烷基，Ar.sub.1.sup.IV和Ar.sub.2.sup.IV相同，分别为从中选择的苯基或取代苯基，##SPC6## 其中R.sub.3.sup.IV为氯、甲氧基或二乙磺酰胺，R.sub.4.sup.IV为氯、甲氧基或三氟甲基，但Ar.sub.1.sup.IV和Ar.sub.2.sup.IV不得为##SPC7## 和化学式Ie的化合物，##EQU9## 其中R.sub.1.sup.V为1至4个碳原子的烷基，R.sub.2.sup.v为1至4个碳原子的烷基，Ar.sub.2.sup.V为苯基，Ar.sub.1.sup.V为从中选择的取代苯基，##SPC8## 其中R.sub.3.sup.v为氯或甲基，R.sub.4.sup.v为氯或甲基。对于上述用途，应用于杂草受感染的地点的化合物量将根据所使用的特定化合物、应用方式、环境条件、要对抗的杂草物种以及涉及的栽培作物而变化。然而，一般来说，应用于地点的适量化合物在1至10公斤/公顷之间，根据需要重复应用。这些化合物可以与除草剂载体或稀释剂一起用作除草剂组合物。这样的组合物也属于本发明。除草剂组合物可用固体或液体应用形式。例如，固体形式，如粉尘形式和颗粒形式，可通过将固体除草剂载体（如硅藻土、高岭土、滑石、白垩、石灰石和纤维素粉）与化合物混合或浸渍而制备。除草剂组合物中可以使用添加剂。典型的添加剂包括湿润和分散剂，例如甲醛与萘磺酸盐的缩聚物和烷基苯磺酸盐，粘附剂，例如糊精，以及乳化稳定剂，例如酪蛋白铵。这些添加剂适合用于混合到湿性粉剂形式的组合物中。除草剂组合物中除了化学式I的活性剂外，还可以含有其他活性剂，例如尿素类、卤代苯甲腈、氨基甲酸酯和三嗪类的除草剂。浓缩形式的组合物通常含有2至80%的化学式I化合物作为活性剂，最好为2至50%。应用形式的组合物通常含有0.01至10%的化学式I化合物作为活性剂。
• US3966805A
  申请人：——

  公开号：US3966805A

  公开（公告）日：1976-06-29
• THE STRUCTURE OF THE SOLID REACTION PRODUCT OF ANILINES AND ETHYL ORTHOFORMATE^1,2
  作者：EDWARD B. KNOTT、ROY A. JEFFREYS

  DOI：10.1021/jo01157a023

  日期：1949.9